US5417942A - Process for trapping gaseous ruthenium on polyvinyl pyridine, more particularly usable for recovering radioactive ruthenium from irradiated nuclear fuels - Google Patents

Process for trapping gaseous ruthenium on polyvinyl pyridine, more particularly usable for recovering radioactive ruthenium from irradiated nuclear fuels Download PDF

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Publication number
US5417942A
US5417942A US08/024,933 US2493393A US5417942A US 5417942 A US5417942 A US 5417942A US 2493393 A US2493393 A US 2493393A US 5417942 A US5417942 A US 5417942A
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United States
Prior art keywords
ruthenium
gas
adsorbent
process according
contacting
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Expired - Lifetime
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US08/024,933
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English (en)
Inventor
Jacques Foos
Marc Lemaire
Alain Guy
Micheline Draye
Rodolph Chomel
Andre Deloge
Pierre Doutreluingne
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Orano Cycle SA
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Compagnie Generale des Matieres Nucleaires SA
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Assigned to COMPAGNIE GENERALE DES MATIERES NUCLEAIRES reassignment COMPAGNIE GENERALE DES MATIERES NUCLEAIRES ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CHOMEL, RODOLPHE, DELOGE, ANDRE, DOUTRELUINGNE, PIERRE, DRAYE, MICHELINE, FOOS, JACQUES, GUY, ALAIN, LEMAIRE, MARC
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/007—Recovery of isotopes from radioactive waste, e.g. fission products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/42—Reprocessing of irradiated fuel
    • G21C19/44—Reprocessing of irradiated fuel of irradiated solid fuel
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/42—Reprocessing of irradiated fuel
    • G21C19/44—Reprocessing of irradiated fuel of irradiated solid fuel
    • G21C19/48—Non-aqueous processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the object of the present invention is a process for the trapping and fixing of ruthenium in gaseous form and in particular ruthenium tetroxide, present in a gaseous flow of an installation for the reprocessing of irradiated nuclear fuels.
  • the irradiation of nuclear fuels in power reactors leads to the production of numerous fission products, whose atomic masses are 70 to 160. These fission products generally appear in the effluents produced at the end of the cycle of the fuel. They in particular include metals of the platinum group such as palladium, rhodium and ruthenium, which are valorizable elements, particularly rhodium due to its use in catalytic converters for cars.
  • ruthenium 106 is one of the main elements contributing to the radioactivity of effluents.
  • a known ruthenium separation process consists of volatilizing the latter in ruthenium tetroxide form by the oxidation of the ruthenium present in nitric solutions using potassium periodate and as is described by BUSH in Platinum Metals Rev, 1991, 35, 4, pp. 202-208.
  • this gaseous ruthenium must then be recovered, which causes problems which have not been solved up to now.
  • the present invention specifically relates to a process for the trapping and fixing of ruthenium in gaseous form, which makes it possible to recover more than 99% of the ruthenium.
  • the process for the recovery of the ruthenium in gaseous form present in a gas consists of contacting the gas with an adsorbent incorporating a vinyl pyridine polymer or copolymer and separating the gas from the adsorbent on which the ruthenium is fixed.
  • the gas containing the ruthenium in gaseous form can in particular be constituted by yapours formed during a volatilization treatment of the ruthenium performed on an aqueous effluent containing fission products from the reprocessing of irradiated nuclear fuels.
  • the invention also relates to a process for the separation of the radioactive ruthenium present in an aqueous effluent containing fission products from the reprocessing of irradiated nuclear fuels and which comprises:
  • This procedure for recovering the ruthenium is particularly advantageous, because it can be used with numerous effluent types, even when the effluents have high salt contents and which can e.g. extend up to 100 g/1.
  • stage a) of the volatilization of ruthenium in ruthenium tetroxide form it is possible to use as the oxidizing agent alkali metal periodate or an alkali metal hypochlorite, such as sodium hypochlorite.
  • the effluent is generally heated to 100° to 150° C.
  • the adsorbents usable in the invention are in particular vinyl pyridine polymers such as poly-4-vinyl pyridine, crosslinked by appropriate crosslinking agents such as divinylbenzene and tetraethylene glycol dimethacrylate. It is also possible to use copolymers of vinyl-4-pyridine and divinylbenzene. Preference is given to the use of crosslinked polyvinyl-4-pyridine with a grain size of 15 to 60 mesh.
  • these crosslinked polyvinyl pyridines have very good ruthenium tetroxide adsorption properties. They also have the advantage of being stable at temperatures up to 260° C. under atmospheric pressure and of resisting reducing and oxidizing agents, so that they can be used in the presence of gases containing constituents such as nitrous yapours, oxygen, chlorine and water vapour. Moreover, they are not sensitive to irradiation, because no degradation is observed after irradiating for 8 hours 24 minutes using a cesium 137 source producing a dose rate of 2 Mrad/h, i.e. 1.05 ⁇ 10 16 MeV/kg.
  • the polyvinyl-4-pyridine used in preferred manner in the invention has a glass transition point of 151° C., which is not modified by irradiation. It can also be used in the form of a powder having an appropriate grain size.
  • working takes place at a temperature above ambient temperature, e.g. at a temperature of the gas on entering the filter of 53° to 63° C.
  • the adsorbent quantity used is dependent on the ruthenium quantity to be extracted and generally 0.07 to 0.5 g of polyvinyl pyridine are used for 1 mCi of Ru.
  • aqueous solution After fixing the .ruthenium to the polyvinyl pyridine, it is possible to recover the latter in aqueous solution, if desired, by treating the polyvinyl pyridine in an appropriate aqueous solution for dissolving the ruthenium in it.
  • a solution can be constituted by a sulphuric acid solution.
  • FIG. 1 An installation for filtering a ruthenium-containing gas.
  • FIG. 2 An installation for the recovery in an aqueous solution of the ruthenium fixed to the adsorbent of the installation of FIG. 1.
  • FIG. 1 shows an installation making it possible to volatilize and then trap the ruthenium present in an aqueous solution of fission products.
  • This installation comprises a reactor (1) able to receive the solution of fission products, which is associated with an oxidizing agent distributor (3) by a pipe equipped with a valve (5).
  • the reactor (1) can be heated by a heating means (7) and the yapours given off are supplied by a pipe (9) to a filter (11) which traps the ruthenium.
  • the latter comprises a sintered product (11a), above which is placed the polyvinyl pyridine powder (11b), which is in turn covered by glass wool (11c).
  • the vapour filtered in the filter (11) is collected in a container (13) and then placed in a safety bottle (15) filled with a soda solution by means of a pipe (17) equipped with a non-return valve (19) and a gas diffuser (21) immersed in the soda solution.
  • the gas bottle (1S) is linked with a venturi (23) making it possible to form a vacuum in the installation.
  • aqueous solution of fission products constituted by a concentrate of fission products and this solution is heated to 100° to 150° C. using the heating means (7) after introducing into it sodium hypochlorite from the distributor (3).
  • the ruthenium is oxidized by the sodium hypochlorite into ruthenium tetroxide, which is volatilized and brought by the pipe (9) together with the gas formed by the yapours from the solution incorporating NO 2 , Ci 2 , H 2 O and O 2 , to the ruthenium filter (11).
  • the temperature of the gas on entering the filter is 58° ⁇ 5° C.
  • the gas is collected in the container (13) and then in the 1N soda-filled safety bottle (15), in which dissolves the ruthenium not fixed to the filter.
  • the ruthenium filter is formed by a vertically positioned, diameter 30 mm glass tube and having a sintered product (11a) on which are deposited 3 g of crosslinked 4-polyvinyl-pyridine having a grain size of 60 mesh and a crosslinking level of 2% and held by glass wool (11c).
  • a sintered product 11a
  • crosslinked 4-polyvinyl-pyridine having a grain size of 60 mesh and a crosslinking level of 2% and held by glass wool (11c).
  • the polyvinyl pyridine powder of the filter (11) is dissolved in sulphuric acid using the installation shown in FIG. 2.
  • This installation comprises a reactor (31) associated with a sulphuric acid distributor (33) by a pipe equipped with a valve (35) and heating means (37).
  • the yapours given off in the reactor (31) can be brought by a pipe (39) into a container (41) connected by a pipe (43) equipped with a non-return valve (45) and a diffuser (46) to a safety bottle (47) containing soda.
  • This safety bottle is associated by a pipe (49) with a venturi (51) for producing a vacuum in the installation.
  • the ruthenium-containing polyvinyl pyridine powder is introduced into the reactor (31) and to it is added concentrated sulphuric acid, followed by heating. During the heating operation, the polyvinyl pyridine is dissolved in the sulphuric acid at the same time as the ruthenium which is not volatile in this medium and the optionally volatilized ruthenium is recovered in the safety bottle (47), where it dissolves in the 1N soda.
  • soda solution of the safety bottle (47) 0.0736 mCi of Ru 106.
  • the ruthenium recovery rate in the sulphuric solution is consequently very high, i.e. 99.8%.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treating Waste Gases (AREA)
US08/024,933 1992-03-03 1993-03-02 Process for trapping gaseous ruthenium on polyvinyl pyridine, more particularly usable for recovering radioactive ruthenium from irradiated nuclear fuels Expired - Lifetime US5417942A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9202514 1992-03-03
FR9202514A FR2688335B1 (fr) 1992-03-03 1992-03-03 Procede de piegeage du ruthenium gazeux sur de la polyvinylpyridine, utilisable en particulier pour recuperer le ruthenium radioactif provenant de combustibles nucleaires irradies.

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US5417942A true US5417942A (en) 1995-05-23

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Country Link
US (1) US5417942A (fr)
EP (1) EP0559536B1 (fr)
JP (1) JP3174190B2 (fr)
KR (1) KR930020487A (fr)
CN (1) CN1076543A (fr)
CA (1) CA2090810A1 (fr)
CZ (1) CZ29293A3 (fr)
DE (1) DE69303640D1 (fr)
FI (1) FI930920A (fr)
FR (1) FR2688335B1 (fr)
SK (1) SK14793A3 (fr)
TW (1) TW274619B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6627770B1 (en) * 2000-08-24 2003-09-30 Celanese International Corporation Method and apparatus for sequesting entrained and volatile catalyst species in a carbonylation process

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2712589B1 (fr) * 1993-11-19 1995-12-29 Cogema Nouveaux hémisépulcrands soufrés et leur utilisation pour l'extraction de métaux, notamment du rhodium .
FR2850878B1 (fr) * 2003-02-10 2005-04-01 Cogema Procede et dispositif de capture de ruthenium present dans un effluent gazeux
JP2004283774A (ja) * 2003-03-24 2004-10-14 Kaken:Kk 燃料電池用触媒とその製造方法
FR2906927B1 (fr) * 2006-10-05 2014-07-25 Commissariat Energie Atomique Procede de vitrification de produits de fission.
CN116836334B (zh) * 2023-08-28 2023-11-28 兰州大学 一种用于分离检测锝的闪烁树脂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5114473A (en) * 1988-08-25 1992-05-19 Union Carbide Chemicals And Plastics Technology Corporation Transition metal recovery
US5131943A (en) * 1990-12-11 1992-07-21 Conoco Inc. Process for the separation of precious group VIII a metals from cyano complexes of such metals and other metals

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6092309A (ja) * 1983-10-25 1985-05-23 Sanyo Chem Ind Ltd 極薄重合体膜の製造法
JPH0715515B2 (ja) * 1985-11-30 1995-02-22 石川島播磨重工業株式会社 オフガス処理装置
JPH0769468B2 (ja) * 1987-04-03 1995-07-31 石川島播磨重工業株式会社 放射性廃棄物からのルテニウム分離方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5114473A (en) * 1988-08-25 1992-05-19 Union Carbide Chemicals And Plastics Technology Corporation Transition metal recovery
US5131943A (en) * 1990-12-11 1992-07-21 Conoco Inc. Process for the separation of precious group VIII a metals from cyano complexes of such metals and other metals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6627770B1 (en) * 2000-08-24 2003-09-30 Celanese International Corporation Method and apparatus for sequesting entrained and volatile catalyst species in a carbonylation process

Also Published As

Publication number Publication date
KR930020487A (ko) 1993-10-19
SK14793A3 (en) 1993-10-06
JPH06138292A (ja) 1994-05-20
JP3174190B2 (ja) 2001-06-11
CZ29293A3 (en) 1994-02-16
FI930920A0 (fi) 1993-03-02
FR2688335B1 (fr) 1994-05-27
EP0559536B1 (fr) 1996-07-17
FR2688335A1 (fr) 1993-09-10
CN1076543A (zh) 1993-09-22
EP0559536A1 (fr) 1993-09-08
TW274619B (fr) 1996-04-21
FI930920A (fi) 1993-09-04
DE69303640D1 (de) 1996-08-22
CA2090810A1 (fr) 1993-09-04

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